A composition comprising methylene malonate monomer and polymer, the preparation thereof and use of the same in underground constructions

Abstract

The present invention relates to a composition comprising methylene malonate monomer and polymer and its use in construction field. Particularly, the invention relates to a composition comprising Component I comprising at least one methylene malonate monomer (A), at least one polymer (B) and at least one acidic stabilizer (C), and Component II comprising at least one alkali accelerator, to the preparation thereof, and to the use of the composition as a protective and/or reinforcement material, particularly used in underground constructions.

1 .- 28 . (canceled) 
     
     
         29 . A two-component composition comprising:
 (1) Component I comprising:
 (A) at least one methylene malonate monomer having formula (I), 
   
       
         
           
           
               
               
           
         
         
           
             wherein, R 1  and R 2  are in each case independently selected from the group consisting of C1-C15-alkyl, C2-C15-alkenyl, C3-C15-cyclolalkyl, C2-C15-heterocyclyl, C2-C15-heterocyclyl-(C1-C15-alkyl), C6-C15-aryl, C6-C15-aryl-C1-C15-alkyl, C2-C15-heteroaryl, C2-C15-heteroaryl-C1-C15-alkyl, C1-C15-alkoxy-C1-C15-alkyl, halo-C1-C15-alkyl, halo-C2-C15-alkenyl, and halo-C3-C15-cyclolalkyl, each of which radicals is optionally substituted, the heteroatom being selected from N, O and S; 
           
           (B) at least one methylene malonate polymer having formula (II), 
         
       
       
         
           
           
               
               
           
         
         
           
             wherein, R 3  and R 4  are, in each case independently selected from the group consisting of C1-C15-alkyl, C2-C15-alkenyl, C3-C15-cyclolalkyl, C2-C15-heterocyclyl, C2-C15-heterocyclyl-C1-C15-alkyl, C6-C15-aryl, C6-C15-aryl-(C1-C15-alkyl), C2-C15-heteroaryl, C2-C15-heteroaryl-C1-C15-alkyl, C1-C15-alkoxy-C1-C15-alkyl, halo-C1-C15-alkyl, halo-C2-C15-alkenyl, and halo-C3-C15-cyclolalkyl, each of which radicals is optionally substituted, the heteroatom being selected from N, O and S, 
             n is an integer from 1 to 20, 
             R 5 , if n=1 is, or if n>1 are in each case independently, selected from the group consisting of C1-C15-alkylene, C2-C15-alkenylene, C2-C15-alkynylene, C6-C15-arylene, C3-C15-cyclolalkylene, C3-C15-cyclolalkenylene, C3-C15-cyclolalkynylene, C2-C15-heterocyclylene, and C2-C15-heteroarylene, each of which radicals is optionally substituted, the heteroatom being selected from N, O and S, wherein R 5  is optionally interrupted by a radical selected from N, O and S; and 
           
           (C) at least one acidic stabilizer; and 
         
         (2) Component II comprising:
 at least one alkali accelerator; 
 wherein, the monomer (A) is in an amount of from 0 to 40 wt. %, preferably from 0 to 30 wt. % and more preferably from 0 to 20 wt. %, and most preferably 0 to 10 wt. %, in each case based on the total weight of the monomer (A) and the polymer (B); 
 the acidic stabilizer (C) is in an amount of from 0.1 to 500 ppm, preferably from 0.1 to 300 ppm and more preferably from 0.1 to 200 ppm, and most preferably from 0.1 to 100 ppm; 
 and 
 the Component II is in an amount of from 0.03 to 100 wt. % based on the total weight of the monomer (A) and the polymer (B); and 
 starting from mixing Component I and Component II, the Shore D hardness of the composition after m hours H t=m  should satisfy the condition: H t=24  is no less than 70, preferably H t=5 ≥80%*H t=24 , more preferably H t=3 ≥70%*H t=24 , even more preferably H t=2 ≥50%*H t=24 . 
 
       
     
     
         30 . The composition according to  claim 29 , wherein the composition has a tensile strength of no less than 7 Mpa and an elongation rate of no less than 1%. 
     
     
         31 . The composition according to  claim 29 , wherein the composition has an adhesive bonding of at least 2 N/mm 2 . 
     
     
         32 . The composition according to  claim 29 , wherein the composition has a gel time of no more than 30 min. 
     
     
         33 . The composition according to  claim 29 , wherein R 1  and R 2  are in each case independently selected from the group consisting of C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cyclolalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, C6-C18-aryl, C6-C18-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl, C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C2-C15-alkenyl and halo-C3-C10-cyclolalkyl, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cyclolalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cyclolalkyl, C6-C10-aryl, C6-C10-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cyclolalkenyl, and C3-C10-cyclolalkynyl, the heteroatom being selected from N, O and S;
 R 3  and R 4  are in each case independently selected from the group consisting of C1-C10-alkyl, C2-C10-alkenyl, C3-C10-cyclolalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, C6-C10-aryl, C6-C10-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C2-C10-heteroaryl-C1-C10-alkyl, C1-C10-alkoxy-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C2-C10-alkenyl, and halo-C3-C10-cyclolalkyl, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cyclolalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cyclolalkyl, C6-C10-aryl, C6-C10-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cyclolalkenyl, and C3-C10-cyclolalkynyl, the heteroatom being selected from N, O and S;   n is an integer from 1 to 15;   R 5 , if n=1 is, or if n>1 are in each case independently, selected from the group consisting of C1-C10-alkylene, C2-C10-alkenylene, C2-C10-alkynylene, C6-C18-arylene, C3-C10-cyclolalkylene, C5-C10-cyclolalkenylene, C5-C10-cyclolalkynylene, C2-C10-heterocyclylene, and C2-C10-heteroarylene, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, C1-C10-alkoxy, C3-C10-cyclolalkyl, C2-C10-heterocyclyl, C2-C10-heterocyclyl-C1-C10-alkyl, halo-C1-C10-alkyl, halo-C3-C10-cyclolalkyl, C6-C10-aryl, C6-C10-aryl-C1-C10-alkyl, C2-C10-heteroaryl, C3-C10-cyclolalkenyl, and C3-C10-cyclolalkynyl, the heteroatom being selected from N, O and S.   
     
     
         34 . The composition according to  claim 29 , wherein R 1  and R 2  are in each case independently selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C3-C6-cyclolalkyl, C3-C6-heterocyclyl, C3-C6-heterocyclyl-C1-C6-alkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C2-C8-heteroaryl, C2-C8-heteroaryl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C2-C6-alkenyl, and halo-C3-C6-cyclolalkyl, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cyclolalkyl, C2-C6-heterocyclyl, C2-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cyclolalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C2-C8-heteroaryl, C3-C6-cyclolalkenyl, and C3-C6-cyclolalkynyl, the heteroatom being selected from N, O and S;
 R 3  and R 4  are in each case independently selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C3-C6-cyclolalkyl, C3-C6-heterocyclyl, C33-C6-heterocyclyl-C1-C6-alkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C2-C8-heteroaryl, C2-C8-heteroaryl-C1-C6-alkyl, C1-C6-alkoxy-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C2-C6-alkenyl, and halo-C3-C6-cyclolalkyl, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cyclolalkyl, C2-C6-heterocyclyl, C2-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cyclolalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C2-C8-heteroaryl, C3-C6-cyclolalkenyl, and C3-C6-cyclolalkynyl, the heteroatom being selected from N, O and S;   n is an integer from 1 to 10;   R 5 , if n=1 is, or if n>1 are in each case independently, selected from the group consisting of C1-C6-alkylene, C2-C6-alkenylene, C2-C6-alkynylene, C6-C8-arylene, C3-C6-cyclolalkylene, C5-C6-cyclolalkenylene, C5-C6-cyclolalkynylene, C2-C6-heterocyclylene, and C3-C6-heteroarylene, each of which radicals is optionally substituted by at least one radical selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-alkoxy, C3-C6-cyclolalkyl, C2-C6-heterocyclyl, C2-C6-heterocyclyl-C1-C6-alkyl, halo-C1-C6-alkyl, halo-C3-C6-cyclolalkyl, C6-C8-aryl, C6-C8-aryl-C1-C6-alkyl, C2-C8-heteroaryl, C3-C6-cyclolalkenyl, and C3-C6-cyclolalkyny, the heteroatom being selected from N, O and S, wherein R 5  is optionally interrupted by a radical selected from N, O and S.   
     
     
         35 . The composition according to  claim 29 , wherein R 1  and R 2  are in each case independently selected from the group consisting of C1-C6-alkyl, C3-C6-cyclolalkyl;
 R 3  and R 4  are in each case independently selected from the group consisting of C1-C6-alkyl;   n is an integer from 1 to 8; and   R 5 , if n=1 is, or if n>1 are in each case independently, selected from the group consisting of C1-C6-alkylene and C6-C8-arylene, each of which radicals is optionally substituted by at least one C1-C6-alkyl.   
     
     
         36 . The composition according to  claim 29 , wherein the acidic stabilizer (C) is at least one selected from sulfuric acid (H 2 SO 4 ), trifluoromethane sulfonic acid (TFA), chlorodifluoro acid, maleic acid, methane sulfonic acid (MSA), p-Toluenesulfonic acid (p-TSA), difluoro acetic acid, trichloroacetic acid, phosphoric acid, dichloroacetic acid and a mixture thereof. 
     
     
         37 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from a base, a base precursor, or a base enhancer. 
     
     
         38 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from aliphatic monoamines, aliphatic diamines, aliphatic triamines, aliphatic oligomer, aromatic amines, etheramines, hydramines, polyurethane catalyst, morpholines, piperidines, piperazines, pyridines, nitro compounds, metal or amine salts of organic lewis acids, preferably, salts of polymer bound acids, 2,4-pentanedionate, diketones, monocarboxylic acids, polyacrylic acid co-polymers, preferably, benzoate salts, propionate salts, salts of amine or metal with mineral acids, preferably, halide, silicate, acetate, chloracetate, metal hydroxide, metal oxide, wherein said metal is preferably at least one selected from lithium, sodium, potassium, magnesium, calcium, copper, iron, zinc, aluminum, and cobalt etc. 
     
     
         39 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from 2-ethylhexylamine, N-Octylamine, tridecylamine mixture of isomers, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, isophorone diamine, neopentanediamine (2,2-Dimethylpropane-1,3-diamine), octamethylenediamine, polyetheramine D 2000, polyetheramine D 230, polyetheramine D 400, polyetheramine T 403, polyetheramine T 5000, 4,4′-diaminodiphenylmethane, benzylamine, dibutylethanolamine, di-(2-ethylhexyl)amine, dibutylamine, dicyclohexylamine, ditridecylamine mixture of isomers, 4,9-Dioxadodecane-1,12-diamine, di-(2-methoxyethyl)amine, N,N-dimethylcyclohexylamine, tributylamine, tripropylamine, tris-(2-ethylhexyl)amine, triethylamine, 2-(diisopropylamino)ethylamine, tetramethyl-1,6-hexanediamine, pentamethyldietylenetriamine, bis(2-dimethylaminoethyl) ether, trimethylaminoethylethanolamine, tris(dimethylaminomethyl)phenol, 2-dimethylaminomethylphenol, dimethylethylamine, dimethylpropylamine, N,N-dimethylisopropylamine, N-Ethyldiisopropylamine, trimethylamine, 3-(cyclohexylamino)propylamine, diethylenetriamine, dipropylene triamine, N3-Amine 3-(2-Aminoethylamino)propylamine, N4-Amine N,N′-Bis-(3-Aminopropyl)ethylenediamine, N,N-Bis-(3-aminopropyl)methylamine, 3-(diethylamino)propylamine, butyldiethanolamine, triisopropanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, N,N-dimethylethanolamine S, N,N-dimethylisopropanolamine, dimethylethanolamine, N,N,N′,N′-Tetrakis(2-hydroxyethyl)ethylenediamine; 3-dimethylaminopropane-1-ol, dimethylaminoethoxyethanol, diethanol-para-toluidine, diisopropanol-p-toluidine, 2,6-xylidine, 2-phenylethylamine, aniline, N-(2-hydroxyethyl)aniline, N,N-di-(2-hydroxyethyl)aniline, N-ethyl-N-(2-hydroxyethyl)aniline, o-toluidine, p-nitrotoluene, N-methylmorpholine, 4-(2-hydroxyethyl)morpholine, 2,2′-Dimorpholinodiethylether, 1,8-diazabicyclo-5,4,0-undecene-7, sodium hydroxide, potassium hydroxide, zinc hydroxide, copper hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, ferric and ferrous hydroxide, sodium benzoate, lithium chloride, sodium acetate, potassium acetate, zinc acetate, copper acetate, magnesium acetate, aluminum acetate, sodium chloracetate, potassium chloracetate, copper chloracetate, zinc chloracetate, magnesium chloracetate, aluminum chloracetate, sodium silicate, potassium silicate, zinc silicate, copper silicate, magnesium silicate, iron silicate and aluminum silicate. 
     
     
         40 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from sodium silicate, potassium silicate, zinc silicate, copper silicate, magnesium silicate, aluminum silicate, dimethylethylamine, dimethylpropylamine, N,N-dimethylisopropylamine, N-Ethyldiisopropylamine, N,N-dimethylcyclohexylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tris-(2-ethylhexyl)amine, 2-(diisopropylamino)ethylamine, tetramethyl-1,6-hexanediamine, S-triazine, pentamethyldietylenetriamine, bis(2-dimethylaminoethyl) ether, N,N-Dimethylcyclohexylamine, bis(2-dimethylaminoethyl)ether, pentamethyldietylenetriamine, trimethylaminoethylethanolamine, tetramethyl-1,6-hexanediamine, tris(dimethylaminomethyl)phenol, 2-dimethylaminomethylphenol, butyldiethanolamine, triisopropanolamine, diethylethanolamine, methyldiethanolamine, methyldiisopropanolamine, N,N-dimethylethanolamine S, N,N-dimethylisopropanolamine, dimethylethanolamine, N,N,N′,N′-Tetrakis(2-hydroxyethyl)ethylenediamine; dimethylaminoethoxyethanol, diethanol-para-toluidine, diisopropanol-p-toluidine, 3-dimethylaminopropane-1-ol, 2,6-xylidine, 2-phenylethylamine, aniline, N-(2-hydroxyethyl)aniline, N,N-di-(2-hydroxyethyl)aniline, N-ethyl-N-(2-hydroxyethyl)aniline, o-toluidine, p-nitrotoluene, lithium chloride, piperidene, piperazine, N-Methylmorpholine, 4-(2-hydroxyethyl)morpholine, 2,2′-Dimorpholinodiethylether, pyridine at a concentration of 0.03-5%. 
     
     
         41 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from sodium propionate, potassium propionate, zinc propionate, copper propionate, magnesium propionate, aluminum propionate, sodium sorbate, potassium sorbate, zinc sorbate, copper sorbate, magnesium sorbate, aluminum sorbate, sodium benzoate, potassium benzoate, zinc benzoate, copper benzoate, magnesium benzoate, aluminum benzoate, 2-ethylhexylamine, N-Octylamine, tridecylamine, 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, isophorone diamine, neopentanediamine, 2,2-Dimethylpropane-1,3-diamine, octamethylenediamine, dibutylethanolamine, 4,4′-diaminodiphenylmethane, benzylamine, polyetheramine D 2000, polyetheramine D 230, polyetheramine D 400, polyetheramine T 403, polyetheramine T 5000, di-(2-ethylhexyl)amine, dibutylamine, dicyclohexylamine, ditridecylamine, 4,9-Dioxadodecane-1,12-diamine, di-(2-methoxyethyl)amine, 3-(cyclohexylamino)propylamine, diethylenetriamine, dipropylene triamine, N3-Amine (3-(2-Aminoethylamino)propylamine), N4-Amine (N,N′-Bis-(3-Aminopropyl)ethylenediamine), 3-(diethylamino)propylamine, N,N-Bis-(3-aminopropyl)methylamine, diketone at a concentration of 0.5-30%. 
     
     
         42 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from sodium hydroxide, potassium hydroxide, zinc hydroxide, copper hydroxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, sodium oxide, potassium oxide, zinc oxide, copper oxide, magnesium oxide, aluminum oxide, calcium oxide, sodium acetate, potassium acetate, zinc acetate, copper acetate, magnesium acetate, aluminum acetate, sodium chloracetate, potassium chloracetate, copper chloracetate, zinc chloracetate, magnesium chloracetate, aluminum chloracetate, ammonium salts, amine salts at a concentration of 5-100%. 
     
     
         43 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from lithium chloride, tris(dimethylaminomethyl)phenol, 2-dimethylaminomethylphenol, diethylenetriamine, N,N,N′,N′-Tetrakis(2-hydroxyethyl)ethylenediamine at a concentration of 0.03-1%. 
     
     
         44 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from sodium propionate, sodium benzoate, 2,2′-Dimorpholinodiethylether at a concentration of 1-35%. 
     
     
         45 . The composition according to  claim 29 , wherein the alkali accelerator is at least one selected from calcium hydroxide, magnesium oxide, Manganese acetylacetonate, tetrabutyl ammonium chloride, tetrabutyl ammonium hydroxide at a concentration of 35-100%. 
     
     
         46 . The composition according to  claim 29 , wherein the composition includes two independent packages of Component I and Component II that may be mixed on the spot for applications of the composition. 
     
     
         47 . A composition according to according to  claim 29 , wherein the composition further comprises at least one optional additive selected from the group consisting of dyes, pigments, toughening agents, impact modifiers, rheology modifiers, plasticizing agents, thixotropic agents, natural or synthetic rubbers, filler agents, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence or other markers, thermal degradation reducers, thermal resistance conferring agents, defoaming agents, surfactants, wetting agents, dispersants, flow or slip aids, biocides, and stabilizers. 
     
     
         48 . A mixture comprising the composition according to  claim 29 . 
     
     
         49 . The mixture according to  claim 48 , wherein the mixture is substantially absence of any solvent. 
     
     
         50 . A process for preparing the composition according to  claim 29  comprising steps of:
 (1) mixing the monomer (A), the polymer (B) and the acidic stabilizer (C) to obtain Component I; 
 (2) preparing the Component II; and 
 (3) mixing the Component I, the Component II to obtain the composition